CN103370276A - Method for preparing a composition including synthetic inorganic particles - Google Patents
Method for preparing a composition including synthetic inorganic particles Download PDFInfo
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- CN103370276A CN103370276A CN2011800626293A CN201180062629A CN103370276A CN 103370276 A CN103370276 A CN 103370276A CN 2011800626293 A CN2011800626293 A CN 2011800626293A CN 201180062629 A CN201180062629 A CN 201180062629A CN 103370276 A CN103370276 A CN 103370276A
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- 239000000203 mixture Substances 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title claims abstract description 81
- 239000010954 inorganic particle Substances 0.000 title description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 117
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 99
- 239000011707 mineral Substances 0.000 claims abstract description 99
- 239000002245 particle Substances 0.000 claims abstract description 88
- 229910052751 metal Inorganic materials 0.000 claims abstract description 68
- 239000002184 metal Substances 0.000 claims abstract description 68
- 238000002360 preparation method Methods 0.000 claims abstract description 43
- 239000000017 hydrogel Substances 0.000 claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 150000007942 carboxylates Chemical class 0.000 claims abstract 9
- 239000000499 gel Substances 0.000 claims description 70
- 229910052732 germanium Inorganic materials 0.000 claims description 56
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 56
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000004108 freeze drying Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 18
- 238000002441 X-ray diffraction Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 229910052604 silicate mineral Inorganic materials 0.000 claims 1
- 230000008961 swelling Effects 0.000 claims 1
- 239000000454 talc Substances 0.000 description 104
- 229910052623 talc Inorganic materials 0.000 description 104
- 235000012222 talc Nutrition 0.000 description 104
- 235000010755 mineral Nutrition 0.000 description 86
- 239000012071 phase Substances 0.000 description 40
- 238000001228 spectrum Methods 0.000 description 39
- -1 elastomerics Substances 0.000 description 34
- 238000001035 drying Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- 235000017281 sodium acetate Nutrition 0.000 description 24
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 22
- 239000001632 sodium acetate Substances 0.000 description 22
- 239000004110 Zinc silicate Substances 0.000 description 13
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 13
- 235000019352 zinc silicate Nutrition 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 230000014509 gene expression Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 230000036571 hydration Effects 0.000 description 8
- 238000006703 hydration reaction Methods 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 229910004283 SiO 4 Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910001510 metal chloride Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 210000002659 acromion Anatomy 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 229910021647 smectite Inorganic materials 0.000 description 3
- 239000010414 supernatant solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- HQAITFAUVZBHNB-UHFFFAOYSA-N sodium;pentahydrate Chemical compound O.O.O.O.O.[Na] HQAITFAUVZBHNB-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 101000879121 Pyrococcus furiosus (strain ATCC 43587 / DSM 3638 / JCM 8422 / Vc1) Sulfide dehydrogenase subunit alpha Proteins 0.000 description 1
- 101000879118 Pyrococcus furiosus (strain ATCC 43587 / DSM 3638 / JCM 8422 / Vc1) Sulfide dehydrogenase subunit beta Proteins 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- UNYOJUYSNFGNDV-UHFFFAOYSA-M magnesium monohydroxide Chemical compound [Mg]O UNYOJUYSNFGNDV-UHFFFAOYSA-M 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- ZHTHGKBAFPDEHL-UHFFFAOYSA-N silicic acid zinc Chemical compound [Zn].[Si](O)(O)(O)O ZHTHGKBAFPDEHL-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/22—Magnesium silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
Abstract
本发明涉及制备包含合成矿物颗粒的组合物的方法，其中：制备所述合成矿物颗粒的水凝胶，使所述水凝胶经历水热处理；其特征在于，至少一个所述水热处理步骤通过向处理介质添加至少一种羧酸盐来进行，所述羧酸盐具有式R-COOM’，其中M’表示选自由Na和K组成的组的金属，并且R选自H和包含少于10个碳原子的烷基基团。
The invention relates to a process for the preparation of a composition comprising synthetic mineral particles, wherein: a hydrogel of said synthetic mineral particles is prepared, said hydrogel is subjected to a hydrothermal treatment; characterized in that at least one of said hydrothermal treatment steps is carried out by adding The treatment medium is carried out with the addition of at least one carboxylate having the formula R-COOM', wherein M' represents a metal selected from the group consisting of Na and K, and R is selected from H and contains less than 10 Alkyl group of carbon atoms.
Description
The present invention relates to prepare the method for the composition that comprises the synthetic mineral particle.
In whole text, " mineral grain ' expression do not comprise carbon, or when needed, only comprises any inorganic particle with the carbon of carbonate or prussiate form.
In whole text, it is lower that " hydrothermal treatment consists " is illustrated in the water existence, in any processing of carrying out under the predetermined temperature and under superatmospheric pressure.
Many mineral for example borate or silicate are used in the various industrial circle.
The phyllosilicate mineral grain, talcum for example, be used in many industrial sectors by for example form with fine granular, such as rubber, thermoplastics, elastomerics, paper, paint, varnish, textiles, metallurgy, pharmacy, cosmetics, phytohygiene product or fertilizer, phyllosilicate talcum for example wherein is by mixing in the composition and use as inert filler (because of its chemical stability or in order to dilute expensive active compound) or functional filler (for example in order to strengthen the mechanical characteristics of some material).
Natural talcum, it is formula Si
4Mg
3O
10(OH)
2Hydroxyl magnesium silicate, belong to phyllosilicate family.Phyllosilicate is made of the irregular stacking of basic scale of crystalline structure, and the number of scale is from several units to tens unit change.Among phyllosilicate (layered silicate), the one group of phyllosilicate that especially comprises talcum, mica and montmorillonite has following characteristics: each basic scale is made of the associating of two tetrahedrallayer that are positioned at octahedral layer both sides.This group is corresponding to phyllosilicate 2/1, and it is the part of smectite especially.From the angle of its structure, phyllosilicate 2/1 is also referred to as T.O.T. (tetrahedron-octahedron-tetrahedron) type.
The octahedral layer of phyllosilicate 2/1 is by C
2-And OH
-(with 2: 1 O
2-/ OH
-Mol ratio) two ion planes form.The tetrahedron net of two dimension is arranged in the both sides in this middle layer, and an one summit is occupied by the oxygen of octahedral layer, and other three are occupied by roughly coplanar oxygen.For example, in natural smectite, tetrahedral site is usually by Si
4+Or Al
3+Ion occupies, and octahedral site is often by positively charged ion Mg
2+, Fe
2+, Al
3+And/or Fe
3+Occupy.Very the smectite octahedron of small proportion and/or tetrahedral site are not occupied and the positively charged ion of the crystal net that forms basic scale are lacked and be responsible for.
About talcum, because the quantity of its application, studied high purity, large layering and particle fineness and narrow granularity and layer and distributed, because they can be conclusive for the quality of the finished product.
Yet, prepare powdered composition by grinding and process from the natural talcum piece of talcum, but can not control purity, layering and the size of the talc particle that obtains.
Under this background, WO2008/009799 provides within 3 days to 30 days time and under 300 ℃-600 ℃ temperature, by the formula (Si with liquid state
xGe
1-x)
4M
3O
11N ' H
2O siliceous/hydrothermal treatment consists of the gel of germanium metal prepares and comprises at least a formula (Si
xGe
1-x)
4M
3O
10(OH)
2Siliceous/method of the talcum composition of the synthetic mineral of germanium metal.In the method according to WO2008/009799, essential in the hydrothermal treatment consists of 300 ℃ of lower 3 day times for the altacite particle that can obtain to have the granularity that between 20nm-100nm, changes, perhaps the hydrothermal treatment consists 600 ℃ of lower 30 day times is essential for the altacite particle that acquisition has 6 μ m level granularity, and the time of hydrothermal treatment consists should be sufficiently long for the particle that allows acquisition to have gratifying degree of crystallinity and thermostability.
Therefore, according to the method for WO2008/009799, although the synthetic mineral that the permission preparation is similar to talcum and its purity can be controlled with regard to productive rate, efficient and profitability, still is difficult to meet high industrial requirements.
The present invention aims to provide the method through improving that preparation comprises the composition of synthetic mineral particle.
The present invention aims to provide the method through improving that preparation comprises the composition of silication synthetic mineral particle.
The present invention aims to provide the composition that preparation comprises the phyllosilicate mineral grain with at least a unexpansive phase, the improvement method of so-called talcum composition.
The present invention aims to provide the method for preparing the talcum composition by the hydrothermal treatment consists of the gel of siliceous/germanium metal, and its time needed hydrothermal treatment consists in the talcum preparation method of composition of describing in the prior art shortens for the time widely.
The present invention also aims to provide the method for composition that preparation comprises the synthetic mineral particle, wherein carries out hydrothermal treatment consists at the hydrogel to the precursor of described synthetic mineral particle under the temperature that lowers and/or in the time that is shortening.
The present invention also aims to provide the method for preparing the talcum composition, wherein carry out the hydrothermal treatment consists of the gel of siliceous/germanium metal under the temperature that lowers and/or in the time that is shortening, and making it possible to obtain to comprise the talcum composition of the phyllosilicate particles of the characteristic with improvement.
The present invention is intended to such method, and its enforcement is simple with fast, and meets the commercial mining restriction.
Target of the present invention also is to provide the method for the such composition of preparation, and described composition comprises the synthetic mineral particle that can be used to replace this type of natural composition in its various application.
Target of the present invention also is to provide the method for the such talcum composition of preparation, and described talcum composition can be used to replace the natural talcum composition in its various application.
The present invention aims to provide the method for talcum composition that preparation has high mineralogy and crystal chemistry purity, and described talcum composition comprises and has layering and thin and low granularity of disperseing and the synthetic mineral particle of thermally-stabilised crystalline structure.
For this reason, the present invention relates to prepare the method for the composition that comprises the synthetic mineral particle, wherein:
The hydrogel of the precursor of the described synthetic mineral particle of-preparation,
-make described hydrogel experience hydrothermal treatment consists,
It is characterized in that, the step of at least one described hydrothermal treatment consists is to be undertaken by add at least a carboxylate salt to treatment media, and described carboxylate salt has formula R-COOM ', wherein:
-M ' expression is selected from the metal of the group that is made of Na and K, and
-R is selected from H and comprises the alkyl group that is less than 10 carbon atoms.
This be because, inventors observe in surprise, the method according to this invention makes it possible to prepare the composition that comprises the synthetic mineral particle, greatly lower simultaneously time and/or the temperature of described hydrothermal treatment consists, wherein in a first step, the hydrogel for preparing the precursor of these synthetic mineral particles, and in second step, carry out the hydrothermal treatment consists of hydrogel by the carboxylate salt that adds at least a for example previously defined formula R-COOM '.
Advantageously and according to the present invention, in the formula R-COOM ' of carboxylate salt, R is selected from H and comprises the alkyl group that is less than 10 carbon atoms, and especially, is selected from hydrogen H-, methyl CH
3-and n-propyl CH
3-CH
2-CH
2-.Therefore, advantageously and according to the present invention, by H-, CH
3-and CH
3-CH
2-CH
2Select R in the group of-formation.
Advantageously and according to the present invention, described synthetic mineral particle is the silication mineral grain, namely belong to the particle of silicate family, its structure comprises tetrahedral [SiO
4] group.Especially, advantageously and according to the present invention, described synthetic mineral particle is the phyllosilicate mineral grain, namely belong to the particle of layered silicate family, it is the part of mica and talcum for example.
In a particularly advantageous embodiment of the method according to this invention, the hydrogel of the precursor of described synthetic mineral particle is formula (Si
xGe
1-x)
4M
3O
11N ' H
2O siliceous/gel of germanium metal:
-M represents that at least one has formula Mg
Y (1)Co
Y (2)Zn
Y (3)Cu
Y (4)My
(8-5)Fe
Y (6)Ni
Y (7)Cr
Y (8)Divalent metal; Each y (i) expression interval [0; 1] real number, and for example
With
-x is interval [0; 1] real number,
-n ' refer to described siliceous/number of the water molecules that the gel of germanium metal associates.
Astoundingly, inventors observe, and the method according to this invention makes it possible to prepare a kind of composition that comprises the phyllosilicate mineral grain, so-called talcum composition, lower widely simultaneously time and/or the temperature of described hydrothermal treatment consists, described method comprises: preparation is by formula (Si
xGe
1-x)
4M
3O
11N ' H
2O siliceous/first step of the hydrogel of the precursor of the gel formation of germanium metal, and in the presence of the carboxylate salt of at least a formula R-COOM ', the siliceous/gel of germanium metal is carried out the second step of hydrothermal treatment consists.To the very wonderful result who obtains by the present invention, can't give any clearly explanation, it allows just to improve widely the speed of hydrothermal treatment consists in the mode identical with catalyzer by the carboxylate salt of adding type R-COOM ' simply in the hydrothermal treatment consists medium.Described siliceous/hydrothermal treatment consists of the gel of germanium metal during, the existence of the carboxylate salt of at least a formula R-COOM ' in the hydrothermal treatment consists medium, seem that nucleus formation and the growth of described phyllosilicate mineral grain are had very important effect, especially by means of its impact on the pH of hydrothermal treatment consists medium, and this is fully in the hydrothermal treatment consists process.
Advantageously and according to the present invention, to the carboxylate salt of described treatment media adding type R-COOM ', in order to have " R-COOM '/hydrogel " mol ratio of for the described hydrogel precursor of described synthetic mineral particle 0.4-100.It is the mol ratio of the amount of the amount of carboxylate salt and hydrogel in the treatment media when hydrothermal treatment consists begins.Should " R-COOM '/hydrogel " ratio can be especially at 1.8-100, especially at 7.2-90 with for example at 40-90.
Prepare therein in the situation of silicate particles, advantageously and according to the present invention, to the carboxylate salt of described treatment media adding type R-COOM ', in order to have " R-COOM '/Si " mol ratio of for silicon 0.1-25.It is the mol ratio of the amount of the amount of carboxylate salt and Siliciumatom in the treatment media when hydrothermal treatment consists begins.This R-COOM '/Si " ratio can be especially at 0.45-25, especially at 1.8-22.5 with for example at 10-22.5.
At least one hydrothermal treatment step is logical to be to carry out to the carboxylate salt that treatment media is added at least a formula R-COOM '.Can with the carboxylate salt of formula R-COOM ', in any moment of hydrothermal treatment consists, for example begin or randomly, after the first step of for example pre-hydrothermal treatment consists, be added in the hydrothermal treatment consists medium.Advantageously and according to the present invention, in described hydrothermal treatment consists at first, to the carboxylate salt of described treatment media adding type R-COOM '.
Advantageously and according to the present invention, to the carboxylate salt of described treatment media adding type R-COOM ', so that with the value of its pH regulator to 8-12.Advantageously and according to the present invention, under 150 ℃-600 ℃ temperature, carry out described hydrothermal treatment consists.The carboxylate salt of at least a formula R-COOM ' seems especially for the hydrothermal treatment consists medium pH that keeps 8-12 and the decline of avoiding pH in the hydrothermal treatment consists process with the existence of (always) concentration of 0.2mol/L-10mol/L in the hydrothermal treatment consists medium.This be because, the inventor observes in surprise, during the hydrothermal treatment consists of the gel of siliceous/germanium metal, the existence of the carboxylate salt of at least a formula R-COOM ' in the hydrothermal treatment consists medium makes it possible to keep the pH of the described medium of 8-12.This effect to pH is different from the effect of damping fluid.Use therein in the situation of sodium acetate, measured pH for example is 9.47 in the hydrothermal treatment consists process, and " acetic acid/acetate ion " right pKa is 4.8.
Carboxylate salt concentration in the adjustment treatment media obtains to comprise the composition of synthetic mineral particle after the time in the hydrothermal treatment consists that shortens with permission.Advantageously and according to the present invention, to the carboxylate salt of described treatment media adding type R-COOM ', so that the concentration of the carboxylate salt for the treatment of media Chinese style R-COOM ' is 0.2mol/L-10mol/L.
Advantageously and according to the present invention, at 150 ℃-600 ℃, particularly carry out described hydrothermal treatment consists under 200 ℃-400 ℃ the temperature.Therefore, in the presence of the carboxylate salt of at least a formula R-COOM ' defined above, at 150 ℃-600 ℃, particularly carry out described hydrothermal treatment consists under 200 ℃-400 ℃ the temperature, make it possible to obtain to comprise the composition of synthetic mineral particle.In addition, by means of the existence of at least a such carboxylate salt, 250 ℃-350 ℃ hydrothermal treatment consists temperature, 300 ℃ temperature for example is enough to obtain to comprise the composition of the phyllosilicate mineral grain with at least a unexpansive phase, so-called talcum composition.By limit its implement in needed energy expenditure, according to talcum preparation method of composition of the present invention therefore than the talcum preparation method of composition that belongs to prior art to environment more friendly (low temperature method).
Advantageously and according to the present invention, adjust the time of hydrothermal treatment consists, especially according in its lower temperature of carrying out hydrothermal treatment consists, in order to allow to obtain described synthetic mineral particle.Advantageously and according to the present invention, make described hydrogel experience hydrothermal treatment consists 30 minutes to 45 days, especially 1 hour to 15 days, particularly 2 hours to 24 hours and time of 2 hours to 12 hours more particularly.
Advantageously and according to the present invention, carry out described hydrogel by means of autoclave, and particularly described siliceous/hydrothermal treatment consists of the gel of germanium metal.It can for example be by nickel-base alloy, for example
Autoclave that (by Haynes International, Kokomo, the U.S. sells) makes, perhaps titanium, or randomly, the hydrothermal treatment consists temperature is no more than in 250 ℃ the situation therein, has the autoclave of the steel of tetrafluoroethylene (PTFE) liner.Such autoclave can have any capacity, for example the capacity from 200mL to 50L.
Advantageously and according to the present invention, under mechanical stirring, carry out described hydrothermal treatment consists.For this reason, can for example use the autoclave that is equipped with the interior metal water screw.
Advantageously and according to the present invention, depress and under agitation carry out described hydrothermal treatment consists at saturation steam.Advantageously and according to the present invention, in autoclave, with described hydrogel, and especially with described siliceous/gel of germanium metal adds such water (preferably, distilled water) amount, it is enough at least in the inner atmosphere that produces saturation steam of this autoclave that brings under the treatment temp.Advantageously and according to the present invention, under abiogenous pressure, namely equaling at least to carry out described hydrothermal treatment consists under the saturation vapor pressure (at the pressure that its lower vapor phase and liquid phase balance each other).Therefore the abiogenous pressure that reaches in autoclave in the hydrothermal treatment consists process especially depend in its lower temperature of described hydrothermal treatment consists, the volume of autoclave and water yield of existence of carrying out.Also possibly, surpassing saturation vapor pressure or surpassing under the pressure of abiogenous pressure, occuring therein to carry out hydrothermal treatment consists in the container of hydrothermal treatment consists.For this reason, injection surface occurs in the autoclave of hydrothermal treatment consists or the container therein to the chemically neutral gas of hydro-thermal reaction.Such gas is selected from by rare gas element (rare gas), particularly argon gas, nitrogen (N
2), the group that consists of of carbonic acid gas and air (pressurized air).By this way, advantageously and according to the present invention, hydrothermal treatment consists is carried out under the pressure of 0.5MPa (5 bar)-20MPa (200 bar).
Advantageously and according to the present invention, (amount of liquid is with cm with liquid/solid ratio liquefaction, that have 2-20, especially 5-15
3Express, the amount of solid is expressed with gram) hydrogel, particularly so siliceous/gel of germanium metal carries out hydrothermal treatment consists.Randomly, if necessary, to liquefaction siliceous/gel of germanium metal adds the water yield that is suitable for reaching this ratio.
On the other hand, advantageously and according to the present invention, described phyllosilicate mineral grain have at least one by phyllosilicate 2/1 type and chemical formula (Si
xGe
1-x)
4M
3O
10(OH)
2The unexpansive phase of stacking formation of basic scale.Especially, in a particularly advantageous embodiment of the method according to this invention, described unexpansive mutually can by phyllosilicate 2/1 type and chemical formula (Si
xGe
1-x)
4M
3O
10(OH)
2, and more particularly, chemical formula Si
4Mg
3O
10(OH)
2The stacking formation of basic scale.
Therefore, in a particularly advantageous embodiment of the method according to this invention, with regard to according to of the present invention siliceous/hydrothermal treatment consists of the gel of germanium metal with regard to, obtain such talcum composition, its form with the colloidal solution that comprises the phyllosilicate mineral grain with at least a unexpansive phase exists.These can so exist with the synthetic mineral particle of the solution in water: or with the mutual state of individuation more or less, or be organized into the more or less coarse aggregate that is formed by the synthetic mineral basic granules of mutual gathering.Especially according to selecting white 150 ℃-600 ℃, particularly be selected from 200 ℃-400 ℃ applied hydrothermal treatment consists temperature, the granularity of these basic granuleses can be in tens nanometers to approximately ten microns variations.
Advantageously and according to the present invention, after hydrothermal treatment consists, reclaim and comprise the colloidal compositions of synthetic mineral particle and make described composition experience drying step.The described composition that comprises the synthetic mineral particle that obtains by the method according to this invention can carry out drying by any powder for drying technology.Advantageously and according to the present invention, and then described hydrothermal treatment consists makes the described synthetic mineral particle drying that obtains by freeze-drying.This drying can also be by means of drying oven, for example under 60 ℃ of other temperature of level, 12 hours in 48 hours, perhaps under microwave radiation, carry out.
In one of the method according to this invention favourable embodiment, by the co-precipitation according to following reaction prepare described siliceous/gel of germanium metal:
M, n ' and (m-n '+1) are positive integer.
Described siliceous/gel of germanium metal can be by using at least a formula MC1
2The coprecipitation reaction of metal chloride prepare.Acquisition is to comprise formula (Si
xGe
1-x)
4M
3O
11N ' H
2The gel of the colloidal solution form of the particle of O exists siliceous/germanium metal.Subsequently need to carry out described siliceous/hydrothermal treatment consists of the gel of germanium metal before, almost completely be substituted in the sodium-chlor that obtains in this coprecipitation process with the carboxylate salt of at least a-especially a kind of and unique-Shi R-COOM '.Advantageously and according to the present invention, add the carboxylate salt of at least a formula R-COOM ' in order to wait mole to replace a NaCl to described treatment media.
The gel of this siliceous/germanium metal is by strong and with following chemical formula ground hydration:
(Si
xG
1-x)
4M
3O
11·n’H
2O，
N ' refers to that high number and its exact value of the water molecules that associates with the gel of this siliceous/germanium metal can be variable and not be known.
In a particularly advantageous embodiment of the method according to this invention, described siliceous/gel of germanium metal has formula Si
4M
3O
11N ' H
2O.In this in situation, described formula Si
4M
3O
11N ' H
2O siliceous/gel of germanium metal is the gel of silicon metal.
Advantageously and according to the present invention, described hydrothermal treatment consists and then makes the described synthetic mineral particle of acquisition, and especially described phyllosilicate particles is dry.Advantageously and according to the present invention, described hydrothermal treatment consists is and then carried out the synthetic mineral particle that obtains by freeze-drying, the drying of especially described phyllosilicate particles.Be included in this dry technology of the phyllosilicate mineral grain in the talcum composition that obtains by the method according to this invention, especially make it possible to the step that grinds that obtains the basic granules of individuation and avoid described particle.
Advantageously, the talcum composition that comprises the phyllosilicate mineral grain with at least a unexpansive phase by prepared according to the methods of the invention has the characteristic diffraction peak of talcum in X-ray diffraction, and particularly is positioned at 9.30
-10.25
The characteristic diffraction peak on the plane of distance (001).Advantageously and according to the present invention, the described composition that comprises the phyllosilicate mineral grain has following characteristic diffraction peak in X-ray diffraction:
-be positioned at 9.50
-10.25
The plane of distance (001);
-be positioned at 4.50
-4.61
The plane of distance (020);
-be positioned at 3.10
-3.20
The plane of distance (003);
-be positioned at 1.50
-1.55
The plane of distance (060);
In addition, advantageously and according to the present invention, described talcum composition also has at least one expansion phase.
In addition, advantageously and according to the present invention, described expansion phase is formed by stacking and at least one interlayer interval between two continuous basic scales of the basic scale of phyllosilicate 2/1 type, described expansion phase has chemical formula:
Si
4M
3-εO
10(OH)
2，(X
r+)
ε′·nH
2O
-X
R+Represent the positively charged ion in the interlayer interval of at least a described basic scale that is present in described expansion mineral facies, so-called interlayer cation,
-r is interval [0; 3] real number and expression positively charged ion X
R+Positive electric charge,
-ε is interval [0; 3] real number and represent the positively charged ion shortage of the basic scale of described expansion phase,
-ε ' is interval [0; 3] real number and expression are present in the interlayer cation X in the interlayer interval of described expansion mineral facies
R+Ratio, and
-n refers to the number of the water molecules that combines with described expansion phase.
Chemical formula Si at expansion phase
4M
3-εO
10(OH)
2, (X
R+)
ε 'NH
2Among the O, n refers to particularly to be present in several water moleculess of being connected with expansion phase in the interlayer interval, with or not with interlayer cation X
R+Combine.
Especially, advantageously and according to the present invention, described talcum composition comprises the phyllosilicate mineral grain that is formed by described expansion phase and interbed between the described unexpansive phase.The talcum composition that comprises the phyllosilicate mineral grain that is formed by such interbed can for example obtain after the hydrothermal treatment consists of carrying out under 150 ℃-300 ℃ temperature.
Such talcum composition experience that comprises by the phyllosilicate mineral grain that forms at expansion phase and interbed between the unexpansive phase is being lower than under the pressure of 5 bar (0.5Mpa), under 300 ℃-600 ℃ temperature, carry out without hydrothermal treatment consists 1-15 hour, especially 2-10 hour, for example 4 hours thermal treatment under 500 ℃-550 ℃ temperature.
Therefore, in an embodiment of the method according to this invention, described hydrothermal treatment consists and then, carry out under 300 ℃-600 ℃ temperature without hydrothermal treatment consists.Making it possible to comprise at least in part talcum composition by the phyllosilicate mineral grain that forms at expansion phase and interbed between the unexpansive phase without hydrothermal treatment consists and change into and comprise only by chemical formula (Si like this
xGe
1-x)
4M
3O
10(OH)
2, and chemical formula Si particularly
4M
3O
10(OH)
2The talcum composition of the unexpansive phyllosilicate mineral grain that forms mutually.
The present invention also relates to prepare the composition that comprises the phyllosilicate mineral grain, the method for so-called talcum composition is characterized in that, completely or partially combination has feature top or cited below.
Other targets of the present invention, advantage and feature be along with to the reading of following description and embodiment and occur, and relate to:
The diffracting spectrum that-accompanying drawing 1 represents corresponding to the X-ray analysis that carries out at the composition that obtains by method of the present invention, and
2 expressions of-accompanying drawing are corresponding to the diffracting spectrum of the X-ray analysis that carries out at the composition that obtains by method of the present invention.
The A/-preparation is according to the general experimental program that comprises the composition of synthetic mineral particle of the present invention
The preparation that comprises the composition of synthetic mineral particle according to the present invention comprises the first step of the hydrogel precursor for preparing described synthetic mineral particle, then be the hydrothermal treatment step of the hydrogel of this precursor, in this process, add the carboxylate salt of at least a formula R-COOM '.
The below has more particularly described the experimental program that preparation comprises the composition of phyllosilicate particles, especially talc particle.
1/-
The preparation of silica gel/germanium metal
The gel of siliceous/germanium metal can be prepared by coprecipitation reaction, and it involves, as reagent, and at least a formula MC1
2Metal chloride.This coprecipitation reaction makes it possible to obtain to have the stoichiometry of talcum, and (4Si, for 3M, M has formula Mg
Y (1)Co
Y (2)Zn
Y (3)Cu
Y (4)Mn
Y (5)Fe
Y (6)Ni
Y (7)Cr
Y (8)) hydration siliceous/gel of germanium metal.
The gel of this siliceous/germanium metal prepares according to the co-precipitation of following reaction equation:
This reaction is implemented from following the beginning:
1. the metasilicate pentahydrate sodium aqueous solution or the sodium metagermanate aqueous solution, perhaps with mol ratio x: the mixture of two kinds of solution of (1-x) this,
2. be diluted in the metal chloride solutions of metal-salt (with the moisture absorption crystallized form) preparation in the distilled water with one or more, and
3.1N hydrochloric acid soln.
The preparation of the gel of this siliceous/germanium metal is undertaken by following following experimental program:
1. mixing salt acid solution and metal chloride solutions,
2. the solution to Starso and/or sodium metagermanate adds this mixture; The co-precipitation gel forms immediately,
3. at centrifugal (3000-7000 rev/min, 5-20 minute, for example 3500 rev/mins, 15 minutes) and after removing supernatant liquor (sodium chloride solution of formation), reclaim gel,
4. water particularly with distilled water or this gel of hypotonic water washing, carries out at least two-wheeled washing/centrifugal simultaneously,
5. centrifugal this gel of rear recovery.
When this finishes fs, obtain strong hydration with the glue denseness siliceous/gel (Si of germanium metal
xGe
1-x)
4M
3O
11N ' H
2O.This gel can have thixotropic behaviour, namely when stirring at that time, changes liquid state into from viscous state, then returns its initial state after certain rest time.
Before making its experience hydrothermal treatment consists, can make the gel drying in the strong hydration of centrifugal rear recovery, for example in drying oven (60 ℃, 2 days), by freeze-drying or pass through drying under microwave radiation.Gel (the Si of siliceous/germanium metal
xGe
1-x)
4M
3O
11N ' H
2The drying of O makes it possible to obtain such powder, its can be stored and before use rehydration so that experience according to hydrothermal treatment consists of the present invention.
2/-is siliceous/gel of germanium metal
Hydrothermal treatment consists
Make drying or undried siliceous/gel (Si of germanium metal
xGe
1-x)
4M
3O
11N ' H
2O, for example the front obtains, and at 150 ℃-600 ℃, and particularly experiences hydrothermal treatment consists under 200 ℃-400 ℃ temperature.
For this reason:
With prior drying or be placed in reactor/autoclave with the gel of liquefied form;
2. under agitation add the solution of the carboxylate salt (with form hydration or anhydrous) that comprises at least a formula R-COOM ' to described gel,
3. randomly, regulate the solid/liquid ratio to 2-20, especially (amount of liquid is with cm for the value of 5-15
3Express, the amount of solid is expressed with gram),
4. under predetermined temperature of reaction, within whole treatment times, reactor/autoclave is placed on drying oven inside.
Randomly, can behind the solution that has added the carboxylate salt that comprises formula R-COOM ', make gel drying, in order to can for example store until the moment of hydrothermal treatment consists.In this case, will need only the gel of the drying that the comprises carboxylate salt liquid/solid ratio of wanting with foundation mixed with water.
Inventors can observe, and the temperature of hydrothermal treatment consists has impact to the granularity of the particle that obtains.This temperature is lower, the particle that is synthesized less (at 300 ℃ of lower tens Nano grades, with for higher temperature approximately ten microns contrast).
Similarly, inventors can notice, and relatively few hydrothermal treatment consists time is enough to allow initial gel agglomerate to change crystallization and heat-staple solid material into.
In the hydrothermal treatment consists process, the gel of siliceous/germanium metal is lost the particulate state crystalline structure that its glue denseness increases in time to take its degree of crystallinity gradually.Observe this material crystallization gradually by X-ray diffraction analysis, it shows as the quick appearance at characteristic peak sharpening and that strengthen fast in treating processes at corresponding diffracting spectrum.
When this hydrothermal treatment consists finishes, obtain to comprise the colloidal talcum composition of the phyllosilicate mineral grain that is suspended in the water.With regard to this hydrothermal treatment consists, by centrifugal (at 3000-7000 rev/min, 5-20 minute) then remove supernatant liquor back and forth packet receiving be contained in gel in the reactor.Supernatant solution comprises the salt of described formula R-COOM ' and can be retained in order to reclaim this carboxylate salt and make its recirculation.
Subsequently, with the gel that reclaims preferably water wash, particularly with distilled water or low infiltration, carry out simultaneously at least two-wheeled washing/centrifugal circulation.
Subsequently, the solids composition of the last time centrifugal rear recovery can be carried out drying:
-under 60 ℃ in drying oven 12 hours, perhaps
-by freeze-drying, for example at CHRIST
In the 1-2LD Plus type Freeze Drying Equipment 48 hours-72 hours.
Obtain at last solids composition separately, its color becomes with the character of the metal chloride of the preparation of the gel that is used for siliceous/germanium metal (same, when needing, the separately ratio of these metal chlorides).
The phyllosilicate mineral grain that is included in the talcum composition that obtains by the method according to this invention has outstanding performance aspect purity, degree of crystallinity and the thermostability, and this is the hydrothermal treatment consists time for needed hydrothermal treatment consists remarkable shortening for the time before in known talcum preparation method of composition.
And then hydrothermal treatment consists, randomly can make the talcum composition experience that obtains under the pressure that is lower than 5 bar (0.5MPa), under 300 ℃-600 ℃ temperature, in 1-15 hour, carry out without hydrothermal treatment consists, if particularly it comprises the phyllosilicate mineral grain that forms by at expansion phase and interbed between the unexpansive phase.Can implement under these circumstances without hydrothermal treatment consists so wherein wanted to change the talcum composition that only comprises by the unexpansive phyllosilicate mineral grain that forms mutually into comprising the talcum composition that contains mineral grain by the phyllosilicate that forms at expansion phase and interbed between the unexpansive phase.
The analysis of B/-constitutional features
Be described below the analytical results of the composition that comprises the synthetic mineral particle that obtains by the method according to this invention.
The below has reported the analytical results by the talcum composition that obtains according to the experimental program of stating previously.These results have affirmed and the invention enables can effectively cause having the constitutional features closely similar with the natural talcum formation of synthetic phyllosilicate mineral grain of (especially layering and degree of crystallinity).They also show, especially by temperature and the selection of the time of enforcement, the invention enables synthesizing stable extremely simply with pure siliceous/the synthetic mineral particle of germanium metal, it has definite and foreseeable size and crystal characteristic.
Analyze and especially carry out by X-ray diffraction with by electron microscope observation.The data of collecting are had in the accompanying drawings and in embodiment 1 to 11, and comment on below.
1/-
X-ray diffraction analysis
In X-ray diffraction, natural talcum is for example known because having especially four distinctive diffraction peaks:
-for plane (001), be positioned at 9.35
A peak of distance;
-for plane (020), be positioned at 4.55
A peak at place;
-for plane (003), be positioned at 3.14
A peak at place;
-for plane (060), be positioned at 1.52
A peak at place.
Fig. 1 has shown to formula Si
4Mg
3O
10(OH)
2The X-ray diffraction of synthetic talc composition in the analytical results that carries out, described composition (for octahedral cations, has Mg according to previously described method
2+), at the gel precipitation of silicon metal, then the sodium acetate with 1mol/L concentration replaces NaCl, and with preparing after 300 ℃ of hydrothermal treatment consists in 6 hours.
Fig. 2 has shown to formula Zn
2SiO
4The X-ray diffraction of composition of synthetic silicic acid zinc in the analytical results that carries out, described composition is in the hydrogel precipitation of the precursor of described zinc silicate particle, prepares after then adding the sodium acetate of 4mol/L concentration and 250 ℃ of hydrothermal treatment consists in 6 hours.
Represented the strength of signal (umber of pulse/second) that becomes with angle of diffraction 2 θ at each RX diffracting spectrum of Fig. 1 and 2.
Especially, the diffracting spectrum that represents among Fig. 1 has had the following 2 θ angle values corresponding to the talcum signal: 5.72 degree; 10.62 degree; 21.65 degree; 22.59 degree; 32.90 degree; 40.10 degree; 41.97 degree; 71.73 degree; 85.40 degree.
The RX diffracting spectrum that represents among Fig. 1 and 2 has been recorded on the CPS120 instrument of being sold by INEL company (Artenay, France).It is the diffractometer with the curve detection device that allows the real-time detection in the hexagonal angle territory.Employed acceleration voltage is that 40kV and strength of current are 25mA.Providing the equidistant Bragg relational expression of structure is: d
Hkl=0.89449/sin θ (using the cobalt anticathode).
Should affirm between the phyllosilicate mineral grain and natural talcum particle of the talcum composition for preparing according to the present invention by the analysis of X-ray diffraction, and between the ore of zinc silicate composition granule for preparing according to the present invention and In Natural Silicate zinc particle, have large structural similarity.
Especially, has the position that fits like a glove with position for the reference diffraction peak of natural talcum corresponding to diffraction peak 3,4 and 5 (Fig. 1) of plane (020), (003) and (060) separately.
About prepared talcum composition, only the diffraction peak 1 of plane (001) and 2 position are different from the position (9.60-10.25 of reference peak slightly
Rather than 9.35
).This value deviation is mainly explained by following:
-nano-scale particle size the size opposite with natural talcum,
The remaining slight hydration of-phyllosilicate mineral grain, its existence owing to the chelating water molecules of talcum scale increased net between apart from d (001), and
-possibly, the character of crystal net octahedral cations.
Yet, should be noted that the deviation that produced by remaining hydration reduces along with longer a little reaction times and more afterburning drying.
At last, the halfwidth degree at the peak of plane (001), (020), (003) and (060) proved according to talcum composition of the present invention siliceous/good crystallinity of the mineral grain of germanium metal.
2/-
The evaluation of microscopic examination and grain graininess
Consideration can consist of the large fineness according to the powder of talcum composition of the present invention, has estimated size and the size-grade distribution of the phyllosilicate mineral grain that forms it by the observation of scanning and field-effect electron microscope and transmission electron microscope.
The granularity of observing basic granules changes between 20nm-100nm.
On the other hand, carried out the measurement according to the specific surface (surface area of the particle relevant with unit mass) of the synthetic mineral particle of measuring by the BET method of argon amount, described argon is adsorbed on the surface of described particle in order to form the unimolecular layer (according to the measurement of BET method, standard A FNOR X11-621 and 622) that covers described surface fully.Observing the specific surface that is included in the phyllosilicate mineral grain in the talcum composition that obtains by the method according to this invention (in the precipitation of the gel of siliceous metal with the sodium acetate replacement NaCl of 1mol/L concentration with 300 ℃ of lower hydrothermal treatment consists of 6 hours, then after the lyophilization) is 175m
2/ g.
Such specific surface value (and the specific surface of natural talcum is 20m
2The separated position (non-gathering) of the stratiform characteristic of the particle that the rank of/g) especially can show low-down granularity, is synthesized, graininess and randomly forms the peeling off of basic scale of described unexpansive phase.
The following examples 1 to 11 for example understand preparation in accordance with the present invention and the composition that comprises the synthetic mineral particle that so obtains, and particularly comprise the constitutional features of the talcum composition of phyllosilicate mineral grain.
Embodiment 1-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
Preparation concentration is the sodium acetate trihydrate CH of 1.3M
3COONa3H
2The aqueous solution of O.The gel that 2g is carried out dry siliceous metal in advance by freeze-drying is dispersed in this sodium acetate solution of 27mL.The suspension that obtains is placed in the airtight titanium reactor.It is in 300 ℃ the stove 6 hours that this titanium reactor is placed on temperature.
After being cooled to envrionment temperature, reactor is opened and the centrifugal suspension that comprises white powder.Reclaim sodium acetate supernatant solution and make its recirculation.
With the white paste of the sodium acetate solution that separates with deionized water wash 2 times, then in the drying oven that brings to 130 ℃ of temperature dry 12 hours.Obtain the 1.13g white solid after dry.
The formula Si that has represented acquisition like this at Fig. 1
4Mg
3O
10(OH)
2The X ray diffracting spectrum of composition of altacite.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 9.717
(I=100) plane of distance (001);
-be positioned at 4.605
(I=9) plane of distance (020);
-be positioned at 3.157
(I=50) plane of distance (003);
-be positioned at 1.525
(I=5) plane of distance (060);
The respective peaks intensity I that provides is carried out stdn with respect to the highest peak of diffracting spectrum, and the intensity of highest peak is considered to equal 100.
Plane (001), plane (020), plane (003) and plane (060) of identifying above the diffraction peak 2,3 that represents on the diffracting spectrum of Fig. 1,4 and 5 corresponds respectively to.
The X ray diffracting spectrum of this talcum composition also have one represent expansion phase corresponding to being positioned at 17.267
The diffraction peak on the plane (001) of (for I=10) distance.
Embodiment 2-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
The method that imitation is described in embodiment 1, wherein working concentration is that three of 0.2M closes aqueous sodium acetate solution and carry out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry by freeze-drying) siliceous/germanium metal under 300 ℃ temperature.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 9.930
(I=100) plane of distance (001);
-be positioned at 4.535
(I=65) plane of distance (020):
-be positioned at 3.178
(I=60) plane of distance (003);
-be positioned at 1.521
(I=32) plane of distance (060);
On the X ray diffracting spectrum of this talcum composition, has a weak acromion corresponding to the diffraction peak of plane (001), the expansion phase that its representative exists with low-down ratio for unexpansive phase.
Embodiment 3-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
The method that imitation is described in embodiment 1, wherein working concentration is that three of 2M closes aqueous sodium acetate solution and carry out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry by freeze-drying) siliceous/germanium metal under 300 ℃ temperature.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 9.704
(I=92) plane of distance (001);
-be positioned at 4.548
(I=100) plane of distance (020);
-be positioned at 3.164
(I=74) plane of distance (003);
-be positioned at 1.521
(I=57) plane of distance (060);
On the X ray diffracting spectrum of this talcum composition, has a weak acromion corresponding to the diffraction peak of plane (001), the expansion phase that its representative exists with low-down ratio for unexpansive phase.
Embodiment 4-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
The method that imitation is described in embodiment 1, wherein working concentration is that three of 1.3M closes aqueous sodium acetate solution and carry out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry by microwave radiation) siliceous/germanium metal under 300 ℃ temperature.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 9.715
(I=100) plane of distance (001);
-be positioned at 4.552
(I=9) plane of distance (020);
-be positioned at 3.149
(I=70) plane of distance (003);
-be positioned at 1.526
(I=9) plane of distance (060);
The X ray diffracting spectrum of this talcum composition also have one represent expansion phase corresponding to being positioned at 18.383
The diffraction peak on the plane (001) of (for I=10) distance.
Embodiment 5-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
The method that imitation is described in embodiment 1, wherein working concentration is that three of 1.3M closes aqueous sodium acetate solution and carry out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry) siliceous/germanium metal under 300 ℃ temperature in drying oven.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 10.088
(I=100) plane of distance (001);
-be positioned at 4.542
(I=50) plane of distance (020);
-be positioned at 3.150
(I=52) plane of distance (003);
-be positioned at 1.523
(I=25) plane of distance (060);
The X ray diffracting spectrum of this talcum composition also have one represent expansion phase corresponding to being positioned at 18.224
The diffraction peak on the plane (001) of (for I=25) distance.
Embodiment 6-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
The method that imitation is described in embodiment 1, wherein working concentration is that three of 4M closes aqueous sodium acetate solution and carry out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry by microwave radiation) siliceous/germanium metal under 300 ℃ temperature.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 9.699
(I=100) plane of distance (001);
-be positioned at 4.557
(I=9) plane of distance (020);
-be positioned at 3.161
(I=30) plane of distance (003);
-be positioned at 1.522
(I=8) plane of distance (060);
The X ray diffracting spectrum of this talcum composition also have one represent expansion phase corresponding to being positioned at 20.239
The diffraction peak on the plane (001) of (for I=5) distance.
Embodiment 7-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
The method that imitation is described in embodiment 1, wherein working concentration is that three of 4M closes aqueous sodium acetate solution and carry out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry) siliceous/germanium metal under 300 ℃ temperature in drying oven.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 9.683
(I=100) plane of distance (001);
-be positioned at 4.566
(I=10) plane of distance (020);
-be positioned at 3.153
(I=35) plane of distance (003);
-be positioned at 1.524
(I=10) plane of distance (060);
The X ray diffracting spectrum of this talcum composition also have one represent expansion phase corresponding to being positioned at 19.840
The diffraction peak on the plane (001) of (for I=9) distance.
Embodiment 8-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
The method that imitation is described in embodiment 1, wherein working concentration is that three of 1.3M closes aqueous sodium acetate solution and carry out the hydrothermal treatment consists 2 hours of the gel of (carrying out in advance dry by freeze-drying) siliceous/germanium metal under 350 ℃ temperature.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 9.899
(I=50) plane of distance (001);
-be positioned at 4.536
(I=100) plane of distance (020);
-be positioned at 3.155
(I=50) plane of distance (003);
-be positioned at 1.515
(I=65) plane of distance (060);
Embodiment 9-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
The method that imitation is described in embodiment 1, wherein working concentration is the potassium acetate CH of 1.3M
3-COOK the aqueous solution also carries out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry by freeze-drying) siliceous/germanium metal under 300 ℃ temperature.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 10.241
(I=100) plane of distance (001);
-be positioned at 4.517
(I=44) plane of distance (020);
-be positioned at 3.315
(I=45) plane of distance (003);
-be positioned at 1.515
(I=20) plane of distance (060);
The X ray diffracting spectrum of this talcum composition also have one represent expansion phase corresponding to being positioned at 12.562
The diffraction peak on the plane (001) of (for I=20) distance.
Embodiment 10-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
The method that imitation is described in embodiment 1, wherein working concentration is the sodium formiate HCOONa aqueous solution of 1.3M and carries out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry by freeze-drying) siliceous/germanium metal under 300 ℃ temperature.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 10.029
(I=90) plane of distance (001);
-be positioned at 4.520
(I=90) plane of distance (020);
-be positioned at 3.170
(I=100) plane of distance (003);
-be positioned at 1.520
(I=70) plane of distance (060);
On the X ray diffracting spectrum of this talcum composition, has an acromion corresponding to the diffraction peak of plane (001), the expansion phase that its representative exists with low-down ratio for unexpansive phase.
Embodiment 11-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
The method that imitation is described in embodiment 1, wherein working concentration is the Sodium propanecarboxylate CH of 1M
3-CH
2-CH
2-COONa the aqueous solution also carries out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry by freeze-drying) siliceous/germanium metal under 300 ℃ temperature.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 10.025
(I=100) plane of distance (001);
-be positioned at 4.510
(1=18) plane of distance (020);
-be positioned at 3.168
(I=75) plane of distance (003);
-be positioned at 1.519
(I=15) plane of distance (060);
On the X ray diffracting spectrum of this talcum composition, has an acromion corresponding to the diffraction peak of plane (001), the expansion phase that its representative exists with low-down ratio for unexpansive phase.
Comparing embodiment 12
The method that imitation is described in embodiment 1 wherein is the magnesium acetate CH of 1.3M with concentration
3-COOMg4H
2O replaces sodium acetate and carry out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry by freeze-drying) siliceous/germanium metal under 300 ℃ temperature.
The X ray diffracting spectrum of the composition that so obtains does not have any diffraction peak corresponding to the talcum diffraction peak.
Comparing embodiment 13
The method that imitation is described in embodiment 1 wherein is the lime acetate CH of 1.3M with concentration
3-COOCaH
2O replaces sodium acetate and carry out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry by freeze-drying) siliceous/germanium metal under 300 ℃ temperature.
The X ray diffracting spectrum of the composition that so obtains does not have any diffraction peak corresponding to the talcum diffraction peak.
Comparing embodiment 14
The method that imitation is described in embodiment 1 wherein is the sodium bicarbonate NaHCO of 1.3M with concentration
3(being commonly referred to the soda heavy carbonic) replaces sodium acetate and carry out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry by freeze-drying) siliceous/germanium metal under 300 ℃ temperature.
The X ray diffracting spectrum of the composition that so obtains does not have any diffraction peak corresponding to the talcum diffraction peak.
Comparing embodiment 15
The method that imitation is described in embodiment 1 wherein is the yellow soda ash Na of 1.3M with concentration
2CO
3Replace sodium acetate and under 300 ℃ temperature, carry out the hydrothermal treatment consists 6 hours of the gel of (carrying out in advance dry by freeze-drying) siliceous/germanium metal.
The X ray diffracting spectrum of the composition that so obtains does not have any diffraction peak corresponding to the talcum diffraction peak.
Neither one makes it possible to after 6 hours, obtaining to comprise the composition of phyllosilicate mineral grain in hydrothermal treatment consists under 300 ℃ the temperature and in the presence of the different carboxylic acids salt at formula R-COOM ' at the hydrothermal condition described in the comparing embodiment 12 to 15.
Comparing embodiment 16
The method that imitation is described in embodiment 1, but in the presence of without any carboxylate salt.The hydrothermal treatment consists of carrying out the gel of (carrying out in advance dry) siliceous/germanium metal under 350 ℃ temperature in drying oven was essential for obtaining the talcum composition in 18 hours.
The X ray diffracting spectrum of this talcum composition has the diffraction peak corresponding to the talcum diffraction peak, and following characteristic diffraction peak particularly:
-be positioned at 9.860
(I=100) plane of distance (001);
-be positioned at 4.533
(I=100) plane of distance (020);
-be positioned at 3.149
(I=81) plane of distance (003);
-be positioned at 1.520
(I=73) plane of distance (060);
Compare with embodiment 5, by using identical initial product (precipitation of the gel of siliceous/germanium metal and the drying of gel in drying oven) simultaneously by raising 50 ℃ hydrothermal treatment consists temperature, should be 18 hours obtaining the talcum composition, rather than in the presence of sodium acetate (1.3M) 6 hours under 300 ℃.
The hydrothermal treatment consists condition of describing respectively in embodiment 1 to 11 all makes it possible to obtain to comprise the composition of the phyllosilicate mineral grain with at least a unexpansive phase.The X-ray diffraction analysis of the different talcum compositions of preparation makes it possible to the certainly existence of unexpansive phase in embodiment 1 to 11, the chemical formula Si that it is identified by characteristic diffraction peak phyllosilicate 2/1 type and that pass through talcum
4M
3O
10(OH)
2The stacking formation of basic scale.
In addition, reach a conclusion from whole previous embodiment: have only formula R-COOM ' (M ' expression is selected from the metal of the group that is comprised of Na, K, be selected from H and comprise the alkyl group that is less than 10 carbon atoms with R) the hydrothermal treatment consists of carboxylate salt under existing, make it possible to the talcum composition that obtains to comprise the phyllosilicate mineral grain with at least a unexpansive phase being less than in 10 hours, for example under the condition described in each of embodiment 1 to 11.
Embodiment 17-preparation is according to the composition that comprises the synthetic mineral particle of the present invention
Preparation formula Zn at first
2SiO
4The hydrogel of precursor of zinc silicate particle.For this reason, on the one hand preparation comprises 10.6g and is dissolved in metasilicate pentahydrate sodium (Na in the 100ml distilled water
2OSiO
25H
2O) solution, and on the other hand, preparation comprise 21.95g and are dissolved in two hydration zinc acetate Zn (CH in the 100ml distilled water
3COO)
2Solution.Under magnetic agitation, add zinc acetate to sodium metasilicate solution.Form immediately white precipitate.
The solution that obtains was under agitation kept 5 minutes, then take turns continuous distilled water wash and the centrifugal hydrogel precursor that reclaims the zinc silicate particle by centrifugal (under 4000 rev/mins, 5 minutes) and 2.
The hydrogel that obtains is added in the distilled water of 100ml and by freeze-drying and carry out drying.
Carry out subsequently the hydrothermal treatment consists of the prepared zinc silicate particle hydrogel precursor in front.For this reason, preparation concentration is the sodium acetate trihydrate CH of 4M
3-COONa3H
2The O aqueous solution.Be dispersed in this sodium acetate solution of 27mL carrying out dry 2g metal silica gel by freeze-drying in advance.The suspension that obtains is placed in the titanium reactor of sealing.This titanium reactor is placed in the stove under 250 ℃ the temperature 6 hours.
Cooling is until after the envrionment temperature, open reactor and the centrifugal suspension that comprises white powder.Reclaim sodium acetate supernatant solution and make its recirculation.
Will be from the isolated white paste of acetate solution with deionized water wash 3 times, then in the drying oven that brings to 130 ℃ of temperature dry 12 hours.Obtain 1.51g white powder solid after dry.
The formula Zn that has represented acquisition like this at Fig. 2
2SiO
4The X ray diffracting spectrum of composition of zinc silicate.
The X ray diffracting spectrum of this zinc silicate composition that represents at Fig. 2 has following diffraction peak:
7.00
(I＝13)；4.03
(I＝26)；3.48
(I＝56)；2.84
(I＝100)；2.63
(I＝80)；2.31
I＝45)；1.86
(I＝30)；1.55
(I＝13)；1.42
(I＝28)；1.36
(I＝13)；1.33
(1＝16)。
The respective peaks intensity I that provides is carried out stdn with respect to the highest peak of diffracting spectrum, and the intensity of highest peak is considered to equal 100.
Zinc silicate Zn
2SiO
4Diffraction peak, for example in corresponding JCPDS card (willemite), define, for following:
6.97
(I＝14)；4.09
(I＝16)；4.02
(I＝33)；3.48
(I＝72)；2.83
(I＝100)；2.63
(I＝86)；2.31
(I＝50)；1.86
(I＝40)；1.55
(I＝17)；1.42
(I＝34)；1.41
(I＝24)；1.36
(I＝18)；1.34
(I＝19)。
Comparing embodiment 18
The method that imitation is described in embodiment 17, but do not having in the presence of the sodium acetate.The hydrothermal treatment consists of carrying out in water (not having silicate) at the hydrogel of the precursor that (carries out in advance) under 250 ℃ the temperature zinc silicate particle in drying oven dry is not enough to obtain formula Zn
2SiO
4The composition of zinc silicate.
This is because the X ray diffracting spectrum of the composition that obtains after hydrothermal treatment consists does not have the diffraction peak corresponding to the zinc silicate diffraction peak.
Therefore, reach a conclusion from embodiment 17 and 18: have only formula R-COOM ' (M ' expression is selected from the metal of the group that is comprised of Na, K, be selected from H and comprise the alkyl group that is less than 10 carbon atoms with R) the synthetic mineral particle of carboxylate salt under existing, zinc silicate Zn for example
2SiO
4The hydrothermal treatment consists of hydrogel of precursor of particle, after the time that shortens and under 250 ℃ temperature, make it possible to obtain to comprise the composition of such zinc silicate particle.
Many other that the present invention can have for embodiment described above and embodiment are used and various version.Especially, described talcum composition can comprise such phyllosilicate mineral grain, and wherein different metals is positioned at octahedral position, for example at (Si
xGe
1-x)
4M
3O
11N ' H
2Among the O, M has formula (Co
0.5Ni
0.5) or (Mg
0.34Cu
0.33Fe
0.33).
Claims (18)
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| FR1005096A FR2969594B1 (en) | 2010-12-23 | 2010-12-23 | PROCESS FOR THE PREPARATION OF A COMPOSITION COMPRISING SYNTHETIC MINERAL PARTICLES |
| PCT/EP2011/073862 WO2012085239A1 (en) | 2010-12-23 | 2011-12-22 | Method for preparing a composition including synthetic inorganic particles |
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| CN108473322A (en) * | 2015-09-28 | 2018-08-31 | 国家科学研究中心 | Synthetic mineral compound, composition containing same and method for preparing same |
| CN112203981A (en) * | 2017-12-22 | 2021-01-08 | 伊梅斯切公司 | Co-synthesis of layered minerals and metal particles and products obtained therefrom |
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| FR2996220B1 (en) * | 2012-09-28 | 2014-09-26 | Centre Nat Rech Scient | PROCESS FOR THE PREPARATION OF A COMPOSITION COMPRISING COLORED SILICATED MINERAL PARTICLES AND A COMPOSITION COMPRISING COLORED SILICATED MINERAL PARTICLES |
| EP2747091A1 (en) | 2012-12-19 | 2014-06-25 | Imerys Talc Europe | Talc composition |
| FR3007405B1 (en) | 2013-06-21 | 2016-07-29 | Centre Nat De La Rech Scient (C N R S ) | PROCESS FOR THE PREPARATION OF A COMPOSITION COMPRISING FUNCTIONALIZED SILICO / GERMANO-METALLIC PARTICLES AND COMPOSITION OBTAINED |
| FR3007752B1 (en) | 2013-06-27 | 2020-03-13 | Centre National De La Recherche Scientifique (C.N.R.S.) | PROCESS FOR THE PREPARATION OF A COMPOSITION COMPRISING FUNCTIONALIZED MINERAL PARTICLES AND COMPOSITION |
| FR3018474B1 (en) | 2014-03-13 | 2019-05-10 | Oberthur Fiduciaire Sas | SECURITY DOCUMENT AND SYNTHETIC PARTICLES |
| FR3028751B1 (en) | 2014-11-24 | 2018-01-05 | L'oreal | POWDER SYNTHETIC PHYLLOSILICATE AS A MATIFYING AGENT AND / OR HOMOGENIZING APPLICATION |
| FR3028753B1 (en) | 2014-11-24 | 2018-01-05 | L'oreal | AQUEOUS OR HYDRO-ALCOHOLIC GEL OF SYNTHETIC PHYLLOSILICATES AS A VISCOSING AGENT, MATIFIING AND / OR HOMOGENIZING APPLICATION |
| JP6553372B2 (en) * | 2015-02-17 | 2019-07-31 | ジェイオーコスメティックス株式会社 | Cosmetics |
| FR3041628B1 (en) * | 2015-09-28 | 2019-07-05 | Centre National De La Recherche Scientifique (C.N.R.S.) | PROCESS FOR PREPARING SYNTHETIC MINERAL PARTICLES AND COMPOSITION COMPRISING SYNTHETIC MINERAL PARTICLES |
| EP3505495A1 (en) | 2017-12-29 | 2019-07-03 | Imertech Sas | Method for preparing synthetic phyllosilicates |
| EP3696144A1 (en) | 2019-02-12 | 2020-08-19 | Imertech Sas | Process for making synthetic minerals |
| CN114229833B (en) * | 2020-09-09 | 2023-04-07 | 哈尔滨金纳科技有限公司 | Preparation method of carbon nanotube material with easy dispersion and high conductivity |
| DE102024121958A1 (en) | 2023-08-11 | 2025-02-13 | Devinochem GmbH & Co.KG | Layered silicate, process for its preparation and its use |
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| CN112203981A (en) * | 2017-12-22 | 2021-01-08 | 伊梅斯切公司 | Co-synthesis of layered minerals and metal particles and products obtained therefrom |
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| CN103370276B (en) | 2016-09-07 |
| EP2655251B1 (en) | 2017-08-02 |
| US9505625B2 (en) | 2016-11-29 |
| WO2012085239A1 (en) | 2012-06-28 |
| ES2646171T3 (en) | 2017-12-12 |
| EP2655251A1 (en) | 2013-10-30 |
| FR2969594B1 (en) | 2013-01-11 |
| FR2969594A1 (en) | 2012-06-29 |
| US20130343980A1 (en) | 2013-12-26 |
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